JP2884280B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having a dyed hydrophilic colloid layer, and more particularly, it has an absorption in the infrared region, is stably present in the photographic material, The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye which is inactive and is easily decolorized in the course of photographic processing.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material, a photographic emulsion layer or other layers are often colored in order to absorb light of a specific wavelength. When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a colored layer is provided on the photographic photosensitive layer on a side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers such as a multilayer color light-sensitive material, a filter layer may be located between them. Light scattered when passing through or after transmission through the photographic emulsion layer is reflected at the boundary between the emulsion layer and the support or on the surface of the support opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing image blur, that is, halation, a coloring layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of a multilayer color light-sensitive material, an antihalation layer may be provided between the layers. In order to prevent a reduction in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation), the photographic emulsion layer is also colored.

On the other hand, in recent years, a recording material sensitized to an infrared wavelength, for example, a recording material for recording an output of a near-infrared laser has been proposed. For example, one of the methods of exposing such a photographic photosensitive material is to scan an original drawing, perform exposure on a silver halide photographic photosensitive material based on the image signal, and form a negative image or a positive image corresponding to the original drawing image. There is known an image forming method using a so-called scanner method for forming.
In this method, as a recording light source of the scanner system,
Semiconductor lasers are most preferably used. This semiconductor laser is small, inexpensive, and easy to modulate.
It has a longer lifespan than other He-Ne lasers and argon lasers and emits light in the infrared region. If a photosensitive material having photosensitivity in the infrared region is used, a bright safelight can be used. It has the advantage to say.

However, the oscillation wavelength of a semiconductor laser is in the red to infrared range, and thus a photosensitive material having high photosensitivity in the red to infrared range is required. Sensitizing dyes for giving spectral sensitivity to this region generally have a broad spectral sensitivity wavelength dependency. Therefore, in a photosensitive material having a plurality of photosensitive layers, each photosensitive layer is formed by a different laser light. It is difficult to selectively expose to light, and so-called color separation deteriorates. Further, when exposure is performed using high-density light such as laser light having a long wavelength in the red to infrared region, light bleeding due to halation or irradiation is large, and the resolution is greatly deteriorated.

A colored layer is used to prevent color separation and resolution degradation. These layers to be colored often consist of hydrophilic colloids, so that for their coloring a water-soluble dye is usually included in the layers. This dye must satisfy the following conditions. (1) To have appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. In other words, the performance of the silver halide photographic emulsion layer must not be adversely affected in a chemical sense, for example, decrease in sensitivity, latent image regression, or fogging. (3) No harmful coloring is left on the processed photographic light-sensitive material by being decolored or dissolved and removed during the photographic processing. (4) Excellent stability over time in a solution or in a photographic material. Many dyes that absorb visible light or ultraviolet light are conventionally known to satisfy such conditions, and are suitable for image-improving purposes in conventional photographic elements sensitized to wavelengths of 700 nm or less. ing. In particular, triarylmethane and oxonol dyes are widely used in this context.

[0006]

Heretofore, many efforts have been made to find a dye satisfying the above conditions, and a large number of dyes have been proposed.

For example, it is described in JP-A Nos. 62-123454, 63-55544, and 64-33547. Tricarbocyanine dye, JP-A-1-22714
Oxonol dyes represented by No. 8
No. 844, merocyanine dyes;
No. 16140, tetraaryl type polymethine dyes, and JP-A-50-100116 and JP-A-62-3
No. 250 and JP-A-2-259753 disclose indoaniline dyes. However, at present, there are very few dyes that can satisfy all the above conditions.
Therefore, there are few excellent photosensitive materials having high photosensitivity in the infrared region, good color separation and prevention of halation and irradiation, and thus make full use of the characteristics of the semiconductor laser having excellent performance as described above. The reality is that you can't do that. An object of the present invention is to provide the above (1)
(2) Infrared-sensitive silver halide photographic photosensitive material containing a dye satisfying the conditions of (3) and (4), having excellent photographic properties, good stability, and leaving no harmful coloring after processing. Is to provide the material.

[0008]

It has been found that the object of the present invention is achieved by a silver halide photographic material containing at least one dye represented by the following general formula [I].

[0009]

Embedded image

In the formula, R ¹ is a hydrogen atom, a halogen atom, a sulfonic acid group, a carboxylic acid group, CONHR, SO ₂ NHR,
A group represented by NHSO ₂ R, NHCOR or NHCONHR (R is an alkyl group, an aryl group or a heterocyclic group); R ² represents a group represented by SO ₂ R, COR or CONHR (R is as defined above); . R ³ and R ⁴ may be the same or different from each other, and include a hydrogen atom, an alkyl group,
Represents an alkoxy group, a hydroxyl group, an amino group or a halogen atom, R ⁵ and R ⁶ may be the same or different, and an alkyl group, an aryl group, an acyl group, a sulfonyl group or a combination of R ⁵ and R ⁶ It may form a 5- or 6-membered ring. Also, R ⁵ and R ⁶ are adjacent R
^{And 4} may be connected to each other to form a 5- or 6-membered ring.
n represents the integer of 0-3. However, it is assumed that the dye molecule has at least four acidic substituents.

The general formula [I] will be described in detail.
The halogen atom represented by R ¹ , R ³ , and R ⁴ is F, Cl, Br. CO represented by R ¹
R in NHR, SO ₂ NHR, NHSO ₂ R, NHCOR and NHCONHR represents an alkyl group, an aryl group or a heterocyclic group, and the alkyl group is an alkyl group having 1 to 5 carbon atoms (eg, a methyl group, an ethyl group, a propyl group). , A butyl group, etc.), and a substituent (for example, a sulfonic acid group,
(A carboxylic acid group, a hydroxyl group, etc.). The aryl group is preferably a phenyl group or a naphthyl group,
Sulfonic acid group, carboxylic acid group, hydroxyl group, halogen atom (F, Cl, Br), alkoxy group having 1 to 5 carbon atoms (for example, methoxy group, ethoxy group, etc.) or amino group (for example, dimethylamino group, di- 4-sulfobutylamino group, dicarboxymethylamino group, etc.). The heterocyclic group is a pyridine ring, 1,3-thiazole ring, 1,3,4-triazole ring, benzothiazole ring, benzimidazole ring, benzoxazole ring,
A 1,2,4-thiadiazole ring or the like is preferable, and a sulfonic acid group, a carboxylic acid group, a hydroxyl group, a methyl group, a methoxy group,
It may be substituted with a halogen atom (F, Cl, Br) or the like.

SO ₂ R, COR or C represented by R ²
R in ONHR has the same meaning as described above. Further, R preferably contains an acidic substituent.

In the present invention, the acidic substituent means a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, SO ₂ NHSO ₂
R or CONHSO ₂ R (R is as defined above);
The sulfonic acid group means a sulfo group or a salt thereof, the carboxylic acid group means a carboxyl group or a salt thereof, and the phosphonic acid group means a phosphono group or a salt thereof. Also,
SO ₂ NHSO ₂ R or CONHSO ₂ R may also be in the form of a salt. Examples of the salt include alkali metal salts such as Na and K, ammonium salts, and organic ammonium salts such as triethylammonium, tributylammonium, pyridinium, and tetrabutylammonium.

The alkyl groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above. Examples of the amino group represented by R ³ and R ⁴ include a di-4-sulfobutylamino group and a dicarboxymethylamino group. The alkoxy group represented by R ³ and R ⁴ preferably has 1 to 5 carbon atoms, and may be substituted with a sulfonic acid group or a carboxylic acid group. (For example, a 4-sulfobutoxy group,
The aryl group represented by R ⁵ and R ⁶ has the same meaning as described above, and the acyl group includes, for example, an acetyl group and a propionyl group, and the sulfonyl group includes a methanesulfonyl group, an ethanesulfonyl group, and the like. Can be done. Further, they may combine with each other to form a pyrrolidine ring, a piperidine ring, a morpholine ring, or the like. Further, R ⁵ and R ⁶ may be bonded to adjacent R ⁴ to form a julolidine ring, a tetrahydroquinoline ring, or the like. However, it is assumed that the dye molecule contains at least four acidic substituents described above.

More preferably, in the general formula [I],
R ¹ is CONHR (R is an alkyl group, an aryl group or a heterocyclic group), R ⁴ is a hydrogen atom and R ⁵ and R
^This has been achieved by a silver halide photographic material having a hydrophilic colloid layer containing at least one dye in which ⁶ is an alkyl group. (Each substituent is as defined above)

Furthermore, it is preferred that the dye molecule contains at least 5 acidic substituents. Particularly, it is preferable that at least two of the acidic substituents in the dye molecule are carboxylic acid groups.

Specific examples of the dye represented by the general formula [I] used in the present invention are shown below, but the scope of the present invention is not limited thereto.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

The compound of the present invention is disclosed in JP-A-50-1001.
No. 16, 62-3250, JP-A-2-129268
No. can be synthesized with reference to the numbers. Next, a synthesis example will be described.

(Synthesis of Compound I-19) 5-Amino-2
2.7 g of-(3,5-disulfophenylcarbamoyl) -1-naphthol, N, N-dimethylacetamide 27
1.9 g of 3,5-dimethoxycarbonylbenzenesulfonyl chloride and 2 ml of pyridine were added to the ml. After stirring at room temperature for 1 hour, 50 ml of ethyl alcohol was added, and the precipitated crystals were separated by filtration. In the crystal, methyl alcohol,
2 g of sodium hydroxide and 10 ml of water were added, and the mixture was boiled under reflux for 1 hour, and 5 g of 5- (3,5-dicarboxyphenylsulfonamido) -2- (3,5-disulfophenylcarbomoyl) -1-naphthol was added. Obtained.

Into 3.3 g of the compound obtained above and 30 ml of methyl alcohol, 1.8 g of the nitroso compound, 2 ml of triethylamine and 2 ml of acetic anhydride were stirred, and after stirring at room temperature for 1 hour, 3.5 g of potassium acetate was added. In addition, the precipitated crystals were separated by filtration. Recrystallization was performed from a mixed solution of water and methyl alcohol to obtain 1.4 g of a dye. Melting point 200 ° C or more λmax (H ₂ O) 738.7 nm, ε
4.73 × 10 ⁴

(Synthesis of Compound I-20) A dye was synthesized in the same manner except that m-chlorosulfonylbenzoyl chloride was used in place of the above 3,5-dimethoxycarbonylbenzenesulfonyl chloride. Melting point 200 ° C or more λmax (H ₂ O) 752.3 nm, ε
4.01 × 10 ⁴ Other compounds can be similarly synthesized.

The dye of the formula [I] is dissolved in a suitable solvent (eg, water, alcohol (eg, methanol, ethanol, etc.) methyl cellosolve, etc., or a mixed solvent thereof), or preferably as an aqueous decomposition product,
It is added to a photosensitive or non-photosensitive coating liquid for a hydrophilic colloid layer. These dyes can be used in combination of two or more kinds.

The use amount of the above-mentioned dye is generally 10 ⁻³ g /
m ² ~2.5g / m ^2, it is possible to find a preferable amount ranges particularly ^{10 -3 g / m 2 ~1.0g /} m 2.

The photographic dye represented by the general formula [I] is particularly effective for the purpose of preventing irradiation, and when used for this purpose, it is mainly added to the emulsion layer. The photographic dyes of the general formula [I] are also particularly effective as antihalation dyes, in which case they are added to the back of the support or between the support and the emulsion layer. General formula [I]
The photographic dyes described above can also be advantageously used as filter dyes.

In the present invention, the dye represented by the general formula [I] is preferably used together with a binder. Hydrophilic colloid materials used as binders include gelatin, gelatin substitutes, collodion, gum arabic, alkyl esters of carboxylated cellulose, cellulose ester derivatives such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, August 1960
Synthetic resins such as the amphoteric copolymers described in U.S. Pat. No. 2,949,442 to Clavier et al., Issued on Jun. 16, 1998, polyvinyl alcohol and other materials well known in the art.

Examples of high molecular gelatin substitutes include copolymers of allylamine with methacrylic acid, copolymers of allylamine with acrylic acid and acrylamide, hydrolyzed copolymers of allylamine with methacrylic acid and vinyl acetate,
A copolymer of allylamine, acrylic acid and styrene,
There are copolymers of allylamine, methacrylic acid and acrylonitrile.

The infrared dye of the present invention can be preferably used in a silver halide photographic material having at least one photosensitive layer having a spectral sensitivity in the infrared region. As such a silver halide photographic light-sensitive material, any material can be used as long as a visible image can be obtained by subjecting a latent image obtained by imagewise exposure to processing such as development, bleaching, fixing, and (transferring). Such materials may be used, and both black and white light-sensitive materials and color light-sensitive materials can be preferably used. In addition, color photographic materials include color paper, color reversal paper, direct positive color paper, color negative film, color reversal film,
Examples include color diffusion transfer photosensitive materials. In particular, it is preferably used for a silver halide photosensitive material which forms an image by scanning exposure using high-density monochromatic light such as a semiconductor laser or an LED.

The silver halide emulsion used in these silver halide light-sensitive materials includes any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like. A silver chlorobromide emulsion is preferable for the purpose of speeding up and simplifying the processing. These silver chlorobromide emulsions may have a surface roughness of 0.01 to 3 as described in JP-A-3-84545 for the purpose of enhancing infrared spectral sensitization sensitivity and stability. High silver chloride grains containing mol% of silver iodide are preferably used. In order to speed up the development processing time, silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

For a light-sensitive material suitable for rapid processing, a so-called high silver chloride emulsion having a high silver chloride content is preferably used. In the present invention, the silver chloride content of the high silver chloride emulsion is 9
It is preferably at least 5 mol%, more preferably at least 97 mol%. Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in a layered or non-layered form inside and / or on the surface of silver halide grains as described above. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and is preferably 20 mol%.
Is more preferable. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains. It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 9
Emulsions of substantially pure silver chloride, such as 8 mol% to 100 mol%, are also preferably used. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average is taken) is from 0.1 μm to 2 μm. Is preferred.

The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion may be one having a regular crystal form such as cubic, tetradecahedral or octahedral, or irregular (irregular) such as spherical or tabular.
A compound having a (regular) crystal form or a compound having these compound forms can be used. Further, it may be composed of a mixture of those having various crystal forms.
In the present invention, among these, the particles having the above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected areas exceed 50% of all grains can be preferably used.

The silver halide emulsion used in the present invention is P.Gl
afkides, Chimie et Phisique Photographique (Paul
Montel, 1967), Photographi by GFDuffin
c Emulsion Chemistry (Focal Press, 1966
Year), Making and Coating Phot by VLZelikman et al
It can be adjusted using a method described in, for example, ographic Emulsion (Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. It is preferable that the localized phase of the silver halide grains of the present invention or the substrate thereof contains a foreign metal ion or a complex ion thereof. Ion selected from iridium, rhodium, iron, etc. or its complex ion for the localized phase, and metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. for the substrate Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. A plurality of these metals may be used. Further, metal ions such as cadmium, zinc, lead, mercury, and thallium can also be used.

The silver halide emulsion used for the photosensitive material for scanning exposure with a laser or the like is suitable for high illuminance exposure and needs a gradation capable of providing a required density within a laser exposure control range.
Further, when infrared spectral sensitization is performed, it is necessary to improve storage stability. For these purposes, it is very useful to use iridium, rhodium, ruthenium or iron ions or complex ions among the above metal ions. The amount of these metal ions or complex ions varies greatly depending on the silver halide emulsion composition, size, doping position, etc. of the doped substrate, but each of iridium and rhodium ions is 5 × 10 ⁻⁹ mol / mol silver. 1 × 10 ^-4
Mole is preferred, and the iron ion is 1 × 10 ⁻⁷ per mole of silver.
Mol to 5 × 10 ^-3 mol is preferably used. These metal ion providing compounds are used during silver halide grain formation.
In a gelatin aqueous solution serving as a dispersion medium, in a halide aqueous solution, in a silver salt aqueous solution or another aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles, etc. The silver halide grains of the present invention are contained in the localized phase and / or other grain portions (substrates). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on where the metal ions are contained in the particles.

The silver halide emulsion used in the present invention is:
Usually, chemical sensitization and spectral sensitization are applied. Chemical sensitization includes chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by addition of an unstable sulfur compound, selenium sensitization by a selenium compound, and tellurium sensitization by a tellurium compound). ), Noble metal sensitization typified by gold sensitization, or reduction sensitization, etc. can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to.
Specific examples of these compounds are described in the above-mentioned JP-A-62-2152.
No. 72, pages 39 to 72, are preferably used. Further, the compounds described in EP0447647 are also preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion in the light-sensitive material of the present invention. When using monochromatic high-density light such as a laser or LED for exposure, it is necessary to spectrally sensitize the light in accordance with the wavelength of these light beams. Spectral sensitization in accordance with this light beam means spectral sensitization using a sensitizing dye having spectral sensitivity at the wavelength of this light beam, and the spectral sensitization sensitivity maximum does not necessarily correspond to the wavelength of this light beam. Does not just mean to match. It is preferable that the wavelength of the light beam and the maximum wavelength of the spectral sensitivity coincide from the viewpoint of sensitivity by these light beams and, in the case of a color photographic material, color separation. It is also preferable to intentionally deviate the luminous flux wavelength from the spectral sensitivity maximum wavelength in order to reduce sensitivity fluctuations due to fluctuations in wavelength, intensity, and the like due to laser temperature changes. Examples of the spectral sensitizing dye used for these spectral sensitizations include, for example, Heterocyclic compounds-Cy by FM Harmer.
anine dyes and relared compounds (John Wiley & Son
s New York, London, 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used.

When a semiconductor laser or LED is used as the scanning exposure light source in the present invention, it is necessary to efficiently sensitize the red to infrared region. In particular, in order to spectrally sensitize a region of 730 nm or more, Japanese Patent Application Laid-Open No. 3-15049
No. 12 upper left column to page 21 lower left column, or JP-A-3-2
No. 0730, page 4, lower left column to page 15, lower left column, EP-0,42
No. 0,011, page 4, line 21 to page 6, line 54, EP-0,42
No. 0,012, page 4, line 12 to page 10, line 33, EP-0,4
Sensitizing dyes described in US Pat. No. 43,466 and US Pat. No. 4,975,362 are preferably used. These sensitizing dyes
It is relatively stable chemically, adsorbs relatively strongly on the surface of silver halide grains, and is resistant to desorption by coexisting dispersions such as couplers. As the sensitizing dye for infrared sensitization, a compound having a reduction potential of −1.05 (V vs. SCE) or a value lower than that is preferable, and a compound having a reduction potential of −1.10 or lower is more preferable. preferable. A sensitizing dye having this property is advantageous for increasing the sensitivity, particularly for stabilizing the sensitivity and for stabilizing the latent image. The reduction potential can be measured by phase discrimination type second harmonic AC polarography. A mercury dropping electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and platinum is used as a counter electrode. Measurement of reduction potential by phase discrimination second harmonic AC voltammetry using platinum as a working electrode is described in "Journal of Imaging Sanence", Journal of Imaging Science, Vol.
Vol., Pp. 27-35 (1986).

In order to incorporate these spectral sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, methylcellosolve, 2,2, It may be dissolved in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent and added to the emulsion. In addition, Tokiko Sho 44-2
No. 3389, JP-B-44-27555, JP-B-57-
An aqueous solution or a colloidal dispersion obtained by coexisting an acid or a base as described in 22089 or the like or an aqueous solution or a colloidal dispersion obtained by coexisting a surfactant as described in US Pat. No. 3,822,135 or US Pat. It may be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. JP-A-53-102733, JP-A-58-105141
The dispersion may be directly dispersed in a hydrophilic colloid as described in the above item, and the dispersion may be added to the emulsion. The timing of addition to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. In other words, before the silver halide emulsion is formed, during the grain formation, immediately after the grain formation, before entering the washing step, before the chemical sensitization, during the chemical sensitization, and immediately after the chemical sensitization until the emulsion is cooled and solidified, during the preparation of the coating solution. , You can choose from. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-628969 and JP-A-4222566, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 28, or can be added before completion of precipitation of silver halide grains to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, spectral sensitizing dyes can be added separately, i.e., some added prior to chemical sensitization and the remainder added after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be in the range of 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles. In the present invention, when using a sensitizing dye having spectral sensitization sensitivity particularly from the red region to the infrared region, it is possible to use compounds described in JP-A-2-157747, page 13, lower right column to page 22, lower right column. preferable. By using these compounds, the preservability of the photographic material, the stability of the processing, and the supersensitizing effect can be specifically enhanced. Among them, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of from 0.5 × 10 ^-5 mol to 5.0 per mol of silver halide.
× 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 5.0.
× 10 ^-3 mol is used and 1 mol per mol of sensitizing dye is used.
There is an advantageous use amount in the range of 1 to 10,000 times, preferably 2 to 5000 times.

There is no particular limitation on the method of exposing the photosensitive material using the dye of the present invention. In other words, surface exposure can be performed using a light source such as ordinary sunlight, a fluorescent lamp, a tungsten lamp or a xenon lamp, but a high-density beam light such as a laser or an LED is moved relative to the photosensitive material. It is preferable to perform scanning digital exposure for exposing an image by causing the image to be exposed. In the case of exposure by scanning exposure, the exposure time of the silver halide in the photosensitive material is the time required for exposing a small area. As the minute area, a minimum unit for controlling the amount of light from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and a realistic range is 50 to 2000 dpi.
It is. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the exposure time is preferably 10 ^-4 seconds or less, more preferably 1 ^-4 seconds or less.
It is the case in the following 0 ^-6 seconds.

The dye of the present invention is used for a color light-sensitive material,
Further, the structure of the photosensitive material when a color image is obtained by scanning exposure will be described in detail. This color photographic material has at least three silver halide emulsion layers on a support,
Preferably, at least one of the layers has spectral sensitivity in the infrared region. As a scanning exposure light source for exposing the color photosensitive material, monochromatic high-density light such as a gas laser, a light emitting diode, a semiconductor laser, a second harmonic generation device combining a semiconductor laser / solid-state laser and a nonlinear optical element, and the like are used. You. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser or a second harmonic generator combining a semiconductor laser / solid laser and a nonlinear optical element. In particular, the use of a semiconductor laser is preferred for designing a device that is compact, inexpensive, and has a long life and high stability. In order to use a semiconductor laser, it is preferable that at least one layer has a spectral sensitivity maximum of 730 nm or more, or at least two layers have a spectral sensitivity maximum of 670 nm or more. This is because the currently available, inexpensive and stable semiconductor laser has an emission wavelength range only in the red to infrared region. However, at the laboratory level, the development of semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology develops, it will be sufficient that these semiconductor lasers can be used stably at low cost. Is expected. In such a case, it is less necessary that at least two layers have a spectral sensitivity maximum at 670 nm or more.

The light-sensitive layer in the color light-sensitive material preferably contains at least one kind of coupler which forms a color by a coupling reaction with an oxidized aromatic amine compound. For a full-color hard copy, the support has at least three kinds of silver halide photosensitive layers having different color sensitivities on a support, and each of the layers is formed by a coupling reaction with an oxidized form of an aromatic amine compound. It is preferable to contain either a coupler that develops magenta or cyan. These three different spectral sensitivities
Although it can be arbitrarily selected depending on the wavelength of the light source used for digital exposure, it is preferable that the nearest spectral sensitivity maximum is separated by at least 30 nm or more. The color-forming couplers (Y, λ) contained in the photosensitive layers (λ ₁ , λ ₂ , λ ₃ ) having at least three different spectral sensitivity maxima.
There is no particular limitation on the correspondence with M, C). That is, 3 × 2
= 6 combinations are possible, but in some cases, it is preferable to use the longest-wavelength photosensitive layer as a yellow coloring layer from the viewpoint of the resolving power of human eyes. The order of coating the photosensitive layers having at least three different spectral sensitivity maximums from the support side is not particularly limited, but from the viewpoint of rapid processing, the photosensitive layer containing silver halide grains having the largest average size is the uppermost layer. It may be preferable to come to Further, from the viewpoint of sharpness, it may be preferable that the photosensitive layer having the longest-wave spectral sensitivity is located on the uppermost layer. In some cases, it is preferable that the lowermost layer be a magenta coloring layer from the viewpoint of the storage stability of the hard copy under light irradiation or the like. Therefore, there are 36 possible combinations of the three different spectral sensitivities, the three color couplers, and the layer order. The present invention can be effectively used for all 36 types of photosensitive materials. Table 1 shows specific examples of the digital exposure light source, the spectral sensitivity maximum, and the color coupler, but the present invention is not limited thereto.

[0048]

[Table 1]

In addition to the infrared dye of the present invention, the light-sensitive material according to the present invention may be coated with a hydrophilic colloid layer in order to prevent irritation and halation and to improve safelight safety and the like, as disclosed in European Patent EP 0 337 490 A2. Dyes (oxonol dyes, cyanine dyes) which can be decolorized by treatment described on pages 27 to 76 of the specification can be used in combination. Further, dyes described in JP-A-2-282244, page 3, from upper right column to page 8, and dyes described in JP-A-3-7931-3
Dyes such as the dyes described in the upper right column of the page to the lower left column of the page 11, which are contained in the state of solid fine particle dispersion in the hydrophilic colloid layer and decolorized by the development treatment, are also preferably used. When these dyes are used, it is preferable to select and use a dye having an absorption that overlaps the spectral sensitivity of the photosensitive layer at its maximum. Using these dyes to make the optical density (logarithm of the reciprocal of transmitted light) at the exposure wavelength of the light-sensitive material (reflection density in the case of a reflective support) 0.5 or more increases sharpness. It is preferable for improvement.

In order to further improve the sharpness, the water-resistant resin layer of the support contains at least 12% by weight (more preferably, at least 12% by weight of titanium oxide surface-treated with dihydric alcohol (eg, trimethylolethane)). 14% by weight or more)
It is preferable to include them. Further, JP-A 1-2395
It is also preferred to use colloidal silver for the antihalation layer as described in US Pat. Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods and processing applied to process this light-sensitive material As additives, the following patent publications, especially European patent EP
No. 0,355,660A2 (Japanese Patent Application No. 1-107011)
No.) those described in the specification are preferably used.

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

When the dye of the present invention is used for a color light-sensitive material, the couplers in the above table are used together with the couplers described in European Patent EP02775.
It is preferable to use a color image storage stability improving compound as described in 89A2. In particular, combination use with a pyrazoloazole coupler is preferred. That is, the compound (F) which forms a chemically inactive and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process, and / or the aromatic remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

As the cyan coupler, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, European Patent EP 0331
No. 85A2, a 3-hydroxypyridine cyan coupler (in particular, a 4-equivalent coupler of the coupler (42) listed as a specific example) having a chlorine leaving group on the 4-equivalent coupler.
Equivalent ones, couplers (6) and (9) are particularly preferred) and cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler example 3, which is listed as a specific example, 8, 34 are particularly preferred)
The use of is also preferred.

The light-sensitive material according to the present invention is provided with a protective agent such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add a fungicide. As the support used in the light-sensitive material according to the present invention, in addition to the supports described in the above table, a white polyester-based support or a layer containing a white pigment for a display may have a silver halide emulsion layer. A support provided on the support may be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. Further, as a support used for the photosensitive material according to the present invention, a transparent support is also preferably used. In this case, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. The exposed photosensitive material is subjected to a conventional developing process.

In the case of a color light-sensitive material, color development processing is performed. For the purpose of rapid processing, bleach-fix processing is preferably performed after color development. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

The processing method of the color light-sensitive material of the present invention includes:
The method described in JP-A-2-207250 is preferred. The processing temperature of the color developer applicable to the present invention is 20 to 5
0 ° C., preferably 30 to 45 ° C. Preferably, the processing time is substantially within 25 seconds. Although the replenishment amount is preferably small, it is suitably 20 to 600 ml, preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably 60-200 ml, most preferably 60-150 ml
It is. In the present invention, the color development time can be arbitrarily determined according to the amount of silver applied to the light-sensitive material, the particle size, etc., but from the viewpoint of rapid processing, it is preferably substantially 45 seconds or less, more preferably Although it is more preferable that the time is within 25 seconds, the term "substantially" as used herein refers to the time from when the photosensitive material enters the developer tank until the photosensitive material enters the next tank. It also includes the time required for the air to travel from the liquid tank to the next tank.

The preferred pH of the washing step or the stabilizing step is 4 to 10, more preferably 5 to 8. The temperature can be variously set depending on the use and characteristics of the photosensitive material, but is generally 30 to 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably it is 10 to 45 seconds, more preferably 10 to 40 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability and the like. A specific preferable replenishment amount is 0.5 to 50 times, preferably 2 to 1 times the carry-in amount from the previous bath per unit area of the light-sensitive material.
5 times. Alternatively, the amount is 300 ml or less, preferably 150 ml or less, per m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be used in the previous step.
As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

When the light-sensitive material of the present invention is a black-and-white light-sensitive material,
Sensitizing dyes described in JP-A-62-123454 (9) to (15) are preferred. Further, supersensitizers and other additives are disclosed in JP-A-62-123454 (15) to (2).
2) applies. Further, as an example of a specific embodiment, JP-A-62-123454 (23) to (25) are applied.

[0063]

【Example】

Example 1 (Preparation of emulsion a) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (2% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate in this aqueous solution, 0.2 mol of sodium chloride and 15 μg of rhodium trichloride
Was added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, silver nitrate was further added to 0.02.
An aqueous solution containing 0.015 mol of potassium bromide, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridate (IV) was added and mixed at 40 ° C. with vigorous stirring. Thereafter, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by settling and desalting. Further, 90.0 g of lime-processed gelatin was added to adjust the pH and pAg of the emulsion to 6.2 and 6.5, respectively. Furthermore, 1 × 10 ⁻⁵ mol / mol Ag of sulfur sensitizer (triethylthiourea) and 1 × 1 of chloroauric acid
0 ^-5 mol / mol Ag and nucleic acid 0.2 g / mol Ag was added, 50
Optimal chemical sensitization was performed at ℃.

With respect to the obtained silver chlorobromide emulsion a, the grain shape, grain size and grain size distribution were determined from an electron micrograph. The silver halide grains contained in the emulsion a were all cubic, and the grain size was 0.52 μm. The variation coefficient of the grain size distribution was 0.08. The particle size is represented by the average value of the diameter of a circle equivalent to the projected area of the particle,
The coefficient of variation of the particle size distribution used was a value obtained by dividing the standard deviation of the size by the average particle size.

Next, the halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from the silver halide crystals. The diffraction angle from the (200) plane was measured in detail using the monochromatic Cukα ray as a radiation source. Diffraction lines from crystals with a uniform halogen composition give a single peak,
Diffraction lines from crystals having localized phases with different compositions give a plurality of peaks corresponding to their compositions. By calculating the lattice constant from the diffraction angle of the measured peak, the halogen composition of the silver halide constituting the crystal can be determined. The measurement result of this silver chlorobromide emulsion a was 10
Observe a broad diffraction pattern centered on silver chloride 70% (silver bromide 30%) and skirted to around 60% silver chloride (silver bromide 40%) in addition to the main peak of 0%. Was completed.

(Preparation of photosensitive material A) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. Thus, a multilayer color photographic paper having the following layer structure was produced. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer 19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-
7) 27.2 cc of ethyl acetate and solvent (So
lv-3) and (Solv-7) 4.1 g each
The solution was added and dissolved, and the resulting solution was diluted with 185% aqueous 10% gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
The resulting mixture was emulsified and dispersed in cc to prepare an emulsified dispersion. On the other hand, a silver chlorobromide emulsion (a) was added to a red-sensitive sensitizing dye (Dye-
An emulsion to which 1) was added was prepared. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In each layer, Cpd-10 and Cpd-11 were used.
Was added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following (Dye-1), (Dye-2), and (Dye-3) were used as spectral sensitizing dyes for each layer.

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow, magenta and cyan color-forming emulsion layers at 8.0 × 10 ^-4 per mol of silver halide. Mole was added. To prevent irradiation, the following dyes were added to the non-photosensitive layer and uniformly dispersed in the film.

[0073]

Embedded image

[0074]

Embedded image

Instead of Dye-A, Dye-B, -C, the dye of the present invention, I-2, I-19, I-20, I-21 and I-22 are dispersed, and the light-sensitive materials (A) to (H) created.

[0076]

Embedded image

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains a white pigment (TiO ₂ ) and a bluish dye (ultra blue)] The first layer (red-sensitive yellow coloring layer) The silver chlorobromide emulsion (a) 0.30 gelatin 1.22 yellow coupler (ExY) 0.82 color image stabilizer (Cpd-1) 0.19 solvent (Solv-3) 0.18 solvent (Solv-7) 0.18 color image stabilizer ( Cpd-7) 0.06

Second layer (color mixture prevention layer) Gelatin 0.64 Color mixture prevention agent (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third layer (infrared-sensitive magenta color-forming layer) Silver chlorobromide emulsion (a) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40

Fourth Layer (Ultraviolet Absorbing Layer) Gelatin 1.41 Ultraviolet Absorbing Agent (UV-1) 0.47 Color Mixing Inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth layer (infrared-sensitive cyan coloring layer) Silver chlorobromide emulsion (a) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent ( Solv-6) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer ( Protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

The following compounds (Cpd-12) and (Cpd-13) were respectively added to the magenta photosensitive layer and the cyan photosensitive layer in an amount of 1.8 × 10 ^-3 mol and 2 × 1 mol per mol of silver halide.
× 10 ^-3 mol was added.

[0094]

Embedded image

(Evaluation of Storage Stability) After the photosensitive material shown in Table 7 prepared by the above method was allowed to stand at 50 ° C. and 80% humidity for 2 days, the reflection absorption spectrum was measured, and the maximum absorption wavelength of each dye was measured. Change rate of light absorptivity (absorptivity after leaving at 50 ° C. and 80% RH / 50 ° C., 80
% RH), and the results are shown in Table 7.

(Evaluation of Decoloring Property) The photosensitive materials shown in Table 7 were subjected to the following image forming treatment, and the reflection absorption spectrum of a white background portion was measured. The residual color ratio of the dye was calculated by comparing the light absorption ratio of the maximum absorption of the dye before and after the image forming process, and the results are shown in Table 7.

The prepared photosensitive material was exposed using the following exposure apparatus. Semiconductor laser AlGaInP (oscillation wavelength, about 6
70 nm), semiconductor laser GaAlAs (oscillation wavelength, about 75
0 nm) and GaAlAs (oscillation wavelength, about 830 nm). Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. The amount of light of the semiconductor laser was controlled by combining a pulse width modulation method for modulating the amount of light by changing the energizing time to the semiconductor laser and an intensity modulation method for modulating the amount of light by changing the amount of current. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 10 ^-7 seconds. After the exposure, the following development processing was performed.

(Development Processing A) The exposed samples were used after being subjected to continuous processing (running) using a paper processing machine until they were replenished with twice the tank capacity of color development in the next processing step. . Processing temperature Temperature Replenisher ^* tank capacity Color development 35 ° C 45 seconds 161 ml 2 liters Bleaching and fixing 30-35 ° C 45 seconds 215 ml 2 liter Rinse 30-35 ° C 20 seconds-1 liter Rinse 30-35 ° C 20 seconds-1 liter rinse 30 to 35 ° C. 20 seconds 350 ml 1 liters drying 70 to 80 ° C. 60 seconds * replenishment rate (set to 3 tank countercurrent system to rinse →.) per photosensitive material 1 m ² had the following composition of each processing solution It is.

Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g -Potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Water is added to 1000 ml 1000 ml pH (25 ° C.) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water is added. 1000ml pH (25 ° C) 6.0 Rinse solution (tank solution and replenisher are the same) Ion exchange water (calcium and magnesium are 3ppm or less each)

Example 2 The light-sensitive material used in Example 1 was evaluated for decolorization using the following processing steps. Table 7 shows the results. (Development process B) Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C 20 seconds 60ml 2 liter Bleach-fix 30-35 ° C 20 seconds 60ml 2 liter Rinse 30-35 ° C 10 seconds -1 liter Rinse 30-35 ° C 10 sec - 1 liter rinse 30 to 35 ° C. 10 seconds 120 ml 1 liter drying 70 to 80 ° C. 20 seconds * replenishment rate (. was 3 tank countercurrent system to rinse →) per photosensitive material 1 m ² of each processing solution The composition is as follows.

Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 4.9 g-potassium carbonate 25 g 37 g 4-Amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline · 2, p-toluenesulfonic acid 12.8 g 19.8 g N, N-bis (carboxymethyl) hydrazine 5.5 g 7.0 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water is added. PH 1000 (25 ° C) 6.0

Rinse solution (tank solution and replenisher are the same) Deionized water (calcium and magnesium are each 3 pp
m or less)

[0105]

[Table 7]

As is evident from Table 7, the conventionally known indoaniline dyes (JP-A-50-100116) are known.
, The performance of the dye of the present invention was excellent in stability and decolorization. Also,
It was found that the sensitivity was less reduced and the resolution was less deteriorated as compared with the comparative dye.

[0107]

From the evaluation results shown in Table 7, it can be seen that the photosensitive material of the present invention has excellent storage stability and little residual color after image forming processing.

Claims (3)

(57) [Claims] 1. A silver halide photographic material comprising at least one dye represented by the following general formula [I]. Embedded image In the formula, R ¹ is a hydrogen atom, a halogen atom, a sulfonic acid group,
Carboxylic acid group, CONHR, SO ₂ NHR, NHSO ₂
A group represented by R, NHCOR or NHCONHR (R
Represents an alkyl group, an aryl group or a heterocyclic group).
R ² represents a group represented by SO ₂ R, COR or CONHR (R is as defined above). R ³ and R ⁴ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an amino group or a halogen atom.
R ⁵ and R ⁶ may be the same or different from each other, and represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group;
R ⁵ and R ⁶ may be linked together to form a 5- or 6-membered ring. Further, R ⁵ and R ⁶ may be mutually connected to adjacent R ⁴ to form a 5- or 6-membered ring. n is 0
Represents an integer of 1 to 3. However, at least 4
Shall have one acidic substituent. 2. In the general formula [I], R ¹ is CONH
R (R represents an alkyl group, an aryl group or a heterocyclic group), R ⁴ is a hydrogen atom, and R ⁵ and R ⁶ have a hydrophilic colloid layer containing at least one dye having an alkyl group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein 3. The silver halide photographic material according to claim 2, wherein the material contains at least 5 acidic substituents in the dye molecule.